EP2334724B1 - Neue elastomere zusammensetzungen mit verbesserter wärmebeständigkeit, verbessertem druckverformungsrest und verbesserter verarbeitbarkeit - Google Patents

Neue elastomere zusammensetzungen mit verbesserter wärmebeständigkeit, verbessertem druckverformungsrest und verbesserter verarbeitbarkeit Download PDF

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EP2334724B1
EP2334724B1 EP09792454.2A EP09792454A EP2334724B1 EP 2334724 B1 EP2334724 B1 EP 2334724B1 EP 09792454 A EP09792454 A EP 09792454A EP 2334724 B1 EP2334724 B1 EP 2334724B1
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acid acceptor
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EP2334724A1 (de
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Victor Nasreddine
Sharon Guo
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Arlanxeo Canada Inc
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Arlanxeo Canada Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/005—Hydrogenated nitrile rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides

Definitions

  • compositions according to the present invention have superior heat resistance, compression set resistance, and improved processability (lower compound Mooney) compared to known hydrogenated nitrile rubber containing compositions.
  • the heat resistance of an elastomer is defined as the maximum temperature at which a given elastomer is capable of operating for an extended period of time, while still retaining its properties.
  • the physical and chemical properties of elastomers exposed to heat and/or air can change and that change can include: (a) additional crosslinking resulting in higher crosslink density and embrittlement of elastomers, (b) chain scission leading to a reduction in chain length and average molecular weight, leading to softening of the material; and (c) chemical alternation of the polymer chain by the formation of polar or other groups.
  • nitrile NBR
  • HNBR nitrile
  • metal catalyst When nitrile (NBR) is hydrogenated to HNBR using a metal catalyst at designated temperatures and pressures, a new polymer is formed that has excellent heat and oil resistance and its properties can be controlled by varying the acrylonitrile level, residual double bonds, and molecular weight. Hydrogenated nitrile elastomers have excellent chemical, oil, and solvent resistance, as well as good aging and heat resistance. HNBR is an improvement over the limitations of NBR, in terms of degradation when exposed to high underhood temperatures in automotive fuel-line components. It also has reduced problems associated with cracking and reduced physical properties. Increasing hydrogenation levels give higher heat and ozone resistance. HNBR is widely used in the automotive market. Examples are belts, hoses, static and dynamic seals. Other areas of application include seals for oil field exploration and processing, and rolls for steel and paper mills.
  • the vulcanization system In addition to the basic polymer chain structure, the vulcanization system also plays a role in the thermal stability. Elastomers vulcanized with peroxides, which form C-C crosslinks, have higher heat resistance as compared to sulfur cured elastomers. This is because the bond energy of C-C is much higher than C-S and polysulfide bonds. Also, heat resistance of sulfur cured elastomers is affected by the length of the sulfur crosslinks. Because of the much weaker polysulfide bonds, vulcanizates with long sulfur crosslinks are more vulnerable to deterioration under heat and oxygen. However, peroxide crosslinking requires special attention to the selection of compounding ingredients. Materials such as plasticizers, oils, and acidic materials can decrease the crosslinking efficiency by competing with the polymer for the free radicals produced by peroxides.
  • the present invention provides a novel elastomeric composition containing an acid acceptor, and a silane-modified mineral additive.
  • Compositions according to the present invention have superior heat resistance at 150° C and higher temperatures, compression set resistance, and improved processability as evidenced by a lower compound mooney, shows excellent heat and compression set resistance after long term aging.
  • the inventive composition also has improved processability.
  • inventive compound that has superior heat resistance, lower compression set, and lower compound mooney.
  • This inventive compound is superior to the compound containing the stabilizer system only. It is also superior to the compound containing the stabilizer and a basic mineral additive known in the art to improve aging.
  • the present invention provides elastomeric composition containing a) a hydrogenated nitrile rubber derived from at least one conjugated diene, at least one ⁇ , ⁇ -unsaturated nitrile and optionally one or more copolymerizable monomers having a Mooney viscosity ML(1+4) 100°C below 55, b) a silane modified wollastonite, c) an acid acceptor and d) a stabilizer system comprised of a hydrogenated nitrile rubber and stabilizer which is selected from the group consisting of a salt of a strong base and a weak acid, a metal salt of a secondary amine or a phenolic salt of a sterically hindered phenolic compound comprising at least two phenolic OH groups.
  • the present invention can also include the use of a heat stabilizing master batch.
  • carboxylated rubber is intended to have a broad meaning and is meant to encompass a rubber having carboxylic groups.
  • Suitable rubbers include XSBR (Styrene-butadiene copolymers and graft polymers with other unsaturated polar monomers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, N- methoxymethyl methacrylic acid amide, N-acetoxymethyl methacrylic acid amide, acrylonitrile, hydroxyethylacrylate and/or hydroxyethylmethacrylate with styrene contents of 2-50 wt. % and containing 1-20 wt.
  • the present invention includes the use of XNBR and/or HXNBR.
  • nitrile rubber or NBR is intended to have a broad meaning and is meant to encompass a copolymer having repeating units derived from at least one conjugated diene, at least one ⁇ , ⁇ -unsaturated nitrile and optionally one or more copolymerizable monomers.
  • Hydrogenated in this invention is preferably understood by more than 50 % of the residual double bonds (RDB) present in the starting nitrile polymer/NBR being hydrogenated, preferably more than 90 % of the RDB are hydrogenated, more preferably greater than 95 % of the RDB are hydrogenated and most preferably more than 99 % of the RDB are hydrogenated.
  • RDB residual double bonds
  • Suitable hydrogenated nitrile polymers also include polymers with a low mooney viscosity. Such polymers are prepared via metathesis reactions as disclosed in U. S. Patent Nos. 7,381,781 ; 6,841,623 ; and 6,780,939 .
  • the conjugated diene may be any known conjugated diene such as a C 4 -C 6 conjugated diene.
  • Preferred conjugated dienes include butadiene, isoprene, piperylene, 2,3-dimethyl butadiene and mixtures thereof. More preferred C 4 -C 6 conjugated dienes are butadiene, isoprene and mixtures thereof. The most preferred C 4 -C 6 conjugated diene is butadiene.
  • the ⁇ , ⁇ -unsaturated nitrile may be any known ⁇ , ⁇ -unsaturated nitrile, such as a C 3 -C 5 ⁇ , ⁇ -unsaturated nitrile.
  • Preferred C 3 -C 5 ⁇ , ⁇ -unsaturated nitriles include acrylonitrile, methacrylonitrile, ethacrylonitrile and mixtures thereof.
  • the most preferred C 3 -C 5 ⁇ , ⁇ -unsaturated nitrile is acrylonitrile.
  • inventive elastomer composition according to the present invention also includes the use of synergistic stabilizer system as specified in claim 1.
  • Preferred stabilizer systems include a salt of a strong base and a weak acid, the salt comprising a metal selected from Group I of the Periodic Table of Elements (according to IVPAC 1985) and an anion selected from the group consisting of carbonic acid, ethylene diamines tetra (acetic) acid, phosphoric acid and mixtures thereof.
  • the weak acids useful in the production of the above-mentioned salt are selected from the group consisting of carbonic acid, C 1 -C 50 fatty acids, ethylene diamine tetra (acetic acid), phosphonic acid and mixtures thereof.
  • the preferred salt for use in the present polymer composition may be selected from the group consisting of sodium carbonate, sodium acetate, sodium phosphate, sodium EDTA, a polycarbodiimide, a carbodiimide, potassium carbonate, sodium stearate, potassium stearate and mixrures thereof.
  • the most preferred salt for use in the present polymer composition is sodium carbonate.
  • Another preferred stabilizer includes a metal salt of a secondary amine, wherein the metal is selected from groups 1 and 2 of the periodic system of the elements according to IUPAC 1985.
  • suitable metals include lithium, sodium, potassium and calcium. Preferred are sodium and potassium.
  • combinations of two or more different metals are also suitable.
  • mixtures of two or more metal secondary amine salts may be used to tailor the properties of the resulting vulcanizate.
  • the secondary amine may be linear or branched and may have substituents.
  • substituents examples include C 1 -C 40 -alkyl groups, C 1 -C 40 -aryl groups, C 1 -C 40 -alkylaryl groups, and C 1 -C 40 -arylalkyl groups.
  • the substituents may contain atoms other than carbon and hydrogen atoms, such as oxygen, sulfur, phosphorous, nitrogen, halogen, or silicon. Examples thereof include alkoxy, aryloxy, alkylthio, arylthio, alkylamines, arylamines, haloalkyl, haloaryl, and many more which will be obvious to one skilled in the art.
  • Non-limiting examples of preferred secondary amines include 4,4'-bis- ⁇ , ⁇ -dimethylbenzyl-diphenylamine (sold as NAUGARD ® 445 by Uniroyal), Octylated diphenyl amine (ODPA) (sold as AGERITE STALITE ® S by R.T.
  • ODPA Octylated diphenyl amine
  • Vanderbilt or styrenated diphenyl amine (sold as WINDSTAY 29 by Goodyear) or 2,4-bis-(n-octylthio)-6,4(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine (sold as IRGANOX ® 565 by Ciba-Geigy) or butylated/octylated diphenylamine (sold as IRGANOX ® 5057 by Ciba-Geigy).
  • the secondary amine may also be cyclic.
  • Cyclic structures can be C 3 -C 40 cycles and contain substituents, heteroatoms and/or aryl groups etc., such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer (TMQ) (sold as VULKANOX ® HS by Bayer).
  • TMQ 2,2,4-trimethyl-1,2-dihydroquinoline polymer
  • the salts useful in this invention can be prepared according to standard procedures known in the art. Such as, by treating a THF solution of the diphenylamine compound with one equivalent of a metal hydride wherein the metal is selected from groups 1 and 2 of the periodic system of elements according to IUPAC 1985. Those skilled in the art will be aware of other methods.
  • a further preferred stabilizer system includes agents based on phenolic salts of sterically hindred phenolic compounds comprising at least two phenolic OH groups. Such agents disclosed in U.S. Patent No. 2004/0092634 .
  • the inventive elastomeric composition according to the present invention contains in the range of about 1-20phr, preferably 1-10phr, more preferablyl-5phr of the stabilizer system.
  • inventive elastomeric composition according to the present invention further contain at least one silane-modified wollastonite.
  • Wollastonites are a naturally occurring calcium silicate mineral with the molecular formula CaSiO 3 . They are white in color, acircular/needle-like, and have an alkaline pH.
  • the Wollastonites used in the Examples of the present invention have aspect ratios of 3:1 to 5:1.
  • the silane used to modify the needle-like/acircular mineral filler preferably belongs to the family of difunctional or polyfunctional silanes having at least two functionalities: one compatible with the filler surface, such as alkoxy groups and a second functionality that compatibilizes the modified filler with the polymer matrix such as a vinyl group in the case of a peroxide-cured recipe.
  • the inventive elastomeric composition according to the present invention contains in the range of 1-200phr, preferably 1-100phr, more preferably 1-50phr of the silane modified mineral filler.
  • the elastomer composition according to the present invention also includes acid acceptors such as metal oxides including magnesium oxide, calcium oxide , and carbonates with alkaline pH.
  • the acid acceptor is added to the composition of the present invention in an amount in the range of 0-200phr, more preferably 0-100phr, and most preferably 0-50phr.
  • the acid acceptor is a divalent metal oxide.
  • carbon black is present in the composition in an amount of in the range of from 20 to 200phr, preferably 30 to 150phr, more preferably 40 to 100phr.
  • carbon black is present in the composition in an amount of in the range of from 20 to 200phr, preferably 30 to 150phr, more preferably 40 to 100phr.
  • the ratio of mineral fillers to carbon black is usually in the range of from 0.05 to 20, preferably 0.1 to 10.
  • the carbon blacks to be used here are prepared by the lamp black, furnace black or gas black process and have preferably BET (DIN 66 131) specific surface areas in the range of from 20 to 200 m2/g, e.g. SAF, ISAF, HAF, FEF or GPF carbon blacks.
  • the rubber elastomer according to the present invention can contain further auxiliary products for rubbers, such as reaction accelerators, vulcanizing accelerators, vulcanizing acceleration auxiliaries, antioxidants, foaming agents, anti-aging agents, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyestuffs, pigments, waxes, extenders, organic acids, inhibitors, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, etc., which are known to the rubber industry.
  • the rubber aids are used in conventional amounts, which depend inter alia on the intended use. Conventional amounts are, e.g., from 0.1 to 50 phr.
  • the composition can contain in the range of 0.1 to 20 phr of an organic fatty acid as an auxiliary product, such as an unsaturated fatty acid having one, two or more carbon double bonds in the molecule which more preferably includes 10% by weight or more of a conjugated diene acid having at least one conjugated carbon-carbon double bond in its molecule.
  • Those fatty acids can have in the range of from 8-22 carbon atoms, or for example from 12-18. Examples include stearic acid, palmitic acid and oleic acid and their calcium-, zinc-, magnesium-, potassium- and ammonium salts.
  • the composition can contain in the range of 5 to 50 phr of an acrylate as an auxiliary product.
  • Suitable acrylates are known from U. S. Patent No. 5,391,627 , from U.S. Patent No. 5,208,294 , see Col. 2,1. 25 to 40, and from U.S. Patent No. 4,983,678 , in particular Col. 2,1. 45 to 62.
  • TTM trimethylolpropane-trimethacrylate
  • BDMA butanedioldimethacrylate
  • EDMA ethylenglycoldimethacrylate
  • metal acrylates in combination with a Scorch-retarder such as sterically hindered phenols (e.g. methyl-substituted aminoalkylphenols, such as 2,6-di-tert.-butyl-4-dimethylaminomethylphenol).
  • a Scorch-retarder such as sterically hindered phenols (e.g. methyl-substituted aminoalkylphenols, such as 2,6-di-tert.-butyl-4-dimethylaminomethylphenol).
  • An antioxidant may be used in preparing a compound according to the present invention.
  • suitable antioxidants include p-dicumyl diphenylamine (NAUGARD ® 445), VULKANOX ® DDA (a diphenylamine derivative), VULKANOX ® ZMB2 (zinc salt of methylmercapto benzimidazole), VULKANOX ® HS (polymerized 1,2-dihydro-2,2,4-trimethyl quinoline) and IRGANOX ® 1035 (thiodiethylene bis(3,5-di-tert.-butyl-4-hydroxy) hydrocinnamate or thiodiethylene bis(3-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionate supplied by Ciba-Geigy.
  • VULKANOX ® is a trademark of Bayer AG.
  • crosslinking agent including commercially available agents including sulfur/sulfur accelerator systems, diamines and peroxides.
  • sulfur/sulfur accelerator systems including sulfur/sulfur accelerator systems, diamines and peroxides.
  • peroxide based vulcanizing agents due to the excellent thermal stability conveyed by the carbon-carbon linkages between polymer chains.
  • Useful peroxide crosslinking agents include dicumyl peroxide (Di-Cup 40KE), di-tert.-butyl peroxide, benzoyl peroxide, 2,2'-bis (tert.-butylperoxy diisopropylbenzene (VULCUP ® 40KE), benzoyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-hexyne-3, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, (2,5-bis(tert.-butylperoxy)-2,5-dimethyl hexane and the like.
  • Di-Cup 40KE dicumyl peroxide
  • di-tert.-butyl peroxide benzoyl peroxide
  • VULCUP ® 40KE 2,2'-bis (tert.-butylperoxy diisopropylbenzene
  • Preferred curing agents are readily determined by means of a few preliminary experiments, which is within the scope of one skilled in the art.
  • a preferred peroxide curing agent is commercially available under the tradename Di-Cup 40KE.
  • the peroxide curing agent (60% active) is suitably used in an amount of 0.1 to 15 parts per hundred parts of rubber (phr), preferably 4 to 10 phr. Too much peroxide may lead to undesirably violent reaction.
  • Vulcanizing co-agents can also be added to the elastomeric composition of the present invention.
  • TAIC triallyl isocyanurate
  • DIAK 7 from DuPont Or N,N'-m-phenylene dimaleimide know as HVA-2 (DuPont Dow)
  • TAC triallyl cyanurate
  • RICON D 153 supplied by Ricon Resins
  • Amounts can be equivalent to the peroxide curative or less, preferably equal.
  • the present invention also includes the use of activators such as zinc peroxide (50% on an inert carrier) using STRUKTOL ZP 1014 in combination with the peroxide. Amounts can be from 0.1 to 15, preferably from 4 to 10phr.
  • the ingredients of the elastomeric composition are often mixed together, suitably at an elevated temperature that may range from 25° C to 200° C. Normally the mixing time does not exceed one hour and a time in the range from 2 to 30 minutes is usually adequate.
  • Mixing is suitably carried out in an internal mixer such as a Banbury mixer, or a Haake or Brabender miniature internal mixer.
  • a two roll mill mixer also provides a good dispersion of the additives within the elastomer.
  • An extruder also provides good mixing, and permits shorter mixing times. It is possible to carry out the mixing in two or more stages, and the mixing can be done in different apparatus, for example one stage in an internal mixer and one stage in an extruder.
  • the elastomeric composition according to the present invention is especially suitable for injection molding articles such as the present invention relates to shaped articles, such as seals, hoses, bearing pads, stators, well head seals, valve plates, cable sheathing, wheels, rollers, pipe seals and couplings.
  • Vulcanization testing was carried out on a Moving Die Rheometer (MDR 2000(E)) using a frequency of oscillation of 1.7 Hz and a 1° arc at 180° C for 60 minutes total run time.
  • the test procedure follows ASTM D-5289.
  • Mooney viscosity was determined at 100° C by preheating the sample 1 minute and then, measuring the torque (Mooney viscosity units) after 4 minutes of shearing action caused by the viscometer disk rotating at 2 r.p.m.. Mooney scorch measurements taken at the time from the lowest torque value to a rise of 5 Mooney units (t05) were carried out at 125 and 135° C.
  • Samples were prepared by curing a macro sheet at 180° C for 13 minutes. Afterwards, samples were died out into standard ASTM die C dumbbells. The test was conducted at 23° C and complies with ASTM D-412 Method A.
  • a tensile sheet cured 14 minutes at 180° C was used to prepare appropriate samples of Die B and Die C geometries. Both tests are designed to give an indication of the resistance to tear of the rubber.
  • the test procedure complies with ASTM D 624.
  • Abrasion resistance is determined according to test method DIN 53 516. The volume loss by rubbing the rubber specimen with an emery paper of defined abrasive power is measured and reported.
  • Hall PLASTHALL ® TOTM Trioctyl Trimellitate
  • KADOX ® 920 is a Zinc Oxide from ZCA (Zinc Corporation of America)
  • DIAK ® 7 (Triallyl isocyanurate) is a coagent from DuPont VULCUP ® 40 KE ( ⁇ -bis(t-butylperoxy)diisopropylbenzene), 40% peroxide Table 2. Properties and aging.
  • MDR CURE CHARACTERISTICS Comp. 1 Ex. 1 Ex.
  • Inventive Example 2 has a faster cure (shorter t90) and good cure characteristics although its MH is lower than Example 1 (not claimed) and Comparative Example 1. It also has improved processability with a lower compound mooney. This can be attributed to the silane modification of the Wollastonite at a microscopic scale which results in better dispersion/incorporation in the rubber matrix compared to Inventive Example 1 where the mineral filler (ZEOLEX ® 23) and silane compatibilizer are added separately. It also shows a lower compression set after long term air aging @ 150° C (2016hrs) as well as at higher temperatures. The long-term air aging data at 150° C and aging at 160° C, 170° C, and 180° C clearly shows that Inventive Example 2 has superior heat resistance compared to Example 1 which has a basic mineral additive known to improve aging.
  • Inventive Example 3 containing (Wollastocoat) has a lower compound mooney of 68 compared to Comparative Example 2 containing ZEOLEX ® 23. It also shows a lower compression set after long term air aging @ 150° C (3024hrs). The long-term air aging data at 150° C and aging at higher test temperatures, as evidenced by the better retention in elongation, clearly shows that Inventive Example 3 has superior heat resistance compared to Comparative Example 2 which has a basic mineral additive known to improve aging. This data confirms the special effect of the Wollastocoat filler in improving heat resistance of HNBR even in the absence of the heat stabilizer package THERBAN ® HT VP KA 8805. Inventive Example 3 also has superior swelling (lower swelling) in water.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Claims (16)

  1. Elastomerzusammensetzung, umfassend
    • a) einen hydrierten Nitrilkautschuk, abgeleitet von wenigstens einem konjugierten Dien, wenigstens einem α,β-ungesättigten Nitril und gegebenenfalls einem oder mehreren copolymerisierbaren Monomeren, mit einer Mooney-Viskosität ML(1+4) bei 100 °C von unter 55,
    • b) einen Silan-modifizierten Wollastonit,
    • c) einen Säureakzeptor und
    • d) ein Stabilisatorsystem bestehend aus
    ∘ einem hydrierten Nitrilkautschuk und
    ∘ Stabilisator, der ausgewählt ist aus der Gruppe bestehend aus
    ▪ einem Salz einer starken Base und einer schwachen Säure,
    ▪ einem Metallsalz eines sekundären Amins und
    ▪ einem Phenolsalz einer sterisch gehinderten Phenolverbindung, die wenigstens zwei phenolische OH-Gruppen umfasst.
  2. Elastomerzusammensetzung gemäß Anspruch 1, wobei der hydrierte Nitrilkautschuk a) ein hydrierter carboxylierter Nitrilkautschuk ist.
  3. Zusammensetzung gemäß Anspruch 1, wobei der Säureakzeptor ein alkalischer Zusatzstoff ausgewählt aus der Gruppe bestehend aus Metalloxiden und Carbonaten ist.
  4. Zusammensetzung gemäß Anspruch 1, worin das Stabilisatorsystem in einer Menge zwischen 5 und 30 phr aufgenommen ist.
  5. Zusammensetzung gemäß Anspruch 1, worin das Stabilisatorsystem in einer Menge zwischen 5 und 20 phr aufgenommen ist.
  6. Zusammensetzung gemäß Anspruch 1, worin der Silanmodifizierte Mineral-Zusatzstoff in einer Menge zwischen 1 und 200 phr aufgenommen ist.
  7. Zusammensetzung gemäß Anspruch 5, worin der Silanmodifizierte Mineral-Zusatzstoff in einer Menge zwischen 1 und 100 phr aufgenommen ist.
  8. Zusammensetzung gemäß Anspruch 1, worin der Säureakzeptor in einer Menge zwischen 0 und 200 phr aufgenommen ist.
  9. Zusammensetzung gemäß Anspruch 8, worin der Säureakzeptor in einer Menge zwischen 0 und 100 phr aufgenommen ist.
  10. Zusammensetzung gemäß Anspruch 9, worin der Säureakzeptor in einer Menge zwischen 0 und 50 phr aufgenommen ist.
  11. Zusammensetzung gemäß Anspruch 1, ferner umfassend einen Härter.
  12. Zusammensetzung gemäß Anspruch 1, ferner umfassend wenigstens einen schwarzen Füllstoff.
  13. Zusammensetzung gemäß Anspruch 1, ferner umfassend Antioxidationsmittel, Antialterungsmittel, Wärmestabilisatoren, Verarbeitungshilfsmittel, Weichmacher, Schaumbildner, Reaktionsbeschleuniger und/oder -aktivatoren oder Vulkanisationsbeschleuniger.
  14. Formkörper, umfassend eine Elastomerzusammensetzung gemäß Anspruch 1.
  15. Zusammensetzung gemäß Anspruch 1, wobei die Veränderung der Dehnung nach wenigstens 2.000 Stunden Altern bei 150 °C weniger als 50 % beträgt.
  16. Zusammensetzung gemäß Anspruch 1, wobei der Kautschuk nach wenigstens 300 Stunden Eintauchen in Wasser eine Quellung von weniger als oder gleich 10 % aufweist.
EP09792454.2A 2008-09-12 2009-09-11 Neue elastomere zusammensetzungen mit verbesserter wärmebeständigkeit, verbessertem druckverformungsrest und verbesserter verarbeitbarkeit Active EP2334724B1 (de)

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Application Number Priority Date Filing Date Title
US9643608P 2008-09-12 2008-09-12
PCT/US2009/056636 WO2010030860A1 (en) 2008-09-12 2009-09-11 Novel elastomeric compositions with improved heat resistance, compression set, and processability

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EP3255088B1 (de) * 2016-06-07 2020-04-29 ARLANXEO Deutschland GmbH Verwendung von vulkanisierbaren zusammensetzungen und vulkanisaten in kontakt mit kühlmittel enthaltend silan-beschichteten wollastonit
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CN102257049A (zh) 2011-11-23
SG194339A1 (en) 2013-11-29
EP2334724A1 (de) 2011-06-22
US20110251320A1 (en) 2011-10-13
CN102257049B (zh) 2014-09-10
KR20110067122A (ko) 2011-06-21
JP2012502174A (ja) 2012-01-26
JP5629686B2 (ja) 2014-11-26
KR101409075B1 (ko) 2014-06-23
US8815984B2 (en) 2014-08-26
CA2736749A1 (en) 2010-03-18
MX2011002605A (es) 2011-09-06
BRPI0918445A2 (pt) 2017-06-13
WO2010030860A1 (en) 2010-03-18

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